Process and apparatus for treating gases



Sept. 23, 1924. 1,509,603

, G. MERSEREAU PROCESS AND APPARATUS FOR TREATING GASES Original Filedsep t. 16, 1913 x\\ K WITNESSES: INVENTOR 5 Mjtubum I BYQM" ATTORNEYPatented Sept. 23, 1924.

UNITED STATES GAIL MERSEREAU, OF NEW YORK, N. Y.,

1,509,603 PATENT OFFICE.

ASSIGNOR, BY MESNE ASSIGNMENTS, TO-

CARBIDE AND CARBON CHEMICALS CORPORATION, A CORPORATION OF NEW YORK.

PROCESS AND APPARATUS FOR TREATING GASES.

A Application filed September 16, 1913, Serial No. 790,0801. RenewedAugust 15, 1918. Serial No. 250,074.

To all whom it may concern.

Be it known that I, GAIL MERSEREAU, a citizen of the United States, andresident of New York, in the county-of'New York and State of New York,have invented a certain new and useful Improved 1 Process and Apparatusfor Treating Gases, of which the following is a specification.

My invention relates to process and apparatus for treating gases.

In many reactions, such for example as treating olefins and diolefinswith chlorin to produce addition products, it is extremely desirabletoaccurately control the temperature at which the reaction takes place.To obtain such" control it is often insuflicient to merely maintain thewalls of the container at a given temperature, for the reactions mayproceed at such a rapid rate that the radiation from the walls and theconvection currents have but a=slight effect at the center of thereceptacle. It therefore becomes desirable to have the reactions takeplace in the intimate presence of a substance of high specific heat. Itis desirable sometimes too, to have a solvent or a catalytic agent.

distributed through 'the space where the reaction is going on. 4

I have found that such desirable effects may be. obtained by having thereactions take place in the presence of a shower or rain of suitableliquid cooled or warmed to the desired temperature. The choice of such aliquid will depend on .the reaction which it is desired to control. Ihave found that where it is desired to chlorinate the above-describedolefins and diolefins with gaseous chlorin, a shower of water or of theliquid chlorinated products themselves will prove a satisfactory coolinor heating agent for controlling the reaction. In the accompanyingdrawing, which shows a section through an apparatus for carrying out myprocess, gases consisting of or compris ing mixed olefins and diolefinsand acetylenes and other gases, many of them saturated, such as may beobtained by the heating or pyrolyzing of many petroleum products underproper conditions, are led from a suitable apparatus through a valvedpipe 1, I

so that they bubble up from a perforated ring 2, through a pool of waterin closed tower 4 or in a tub or tank 3, in which is submerged the baseof a cl sed chamber or tower 4.

This tower I have found will last fairly well if made even of pineboards, but it may be made of terra cotta or metal lined with plasticmaterial, or of steel, copper, lead, etc., or other metal alone, or ofother suitable material.

The gases, as they bubble up through the pool of water, catchand unitewith a gaseous halogen suchl as chlorin which is bubbling from aperforated ring 5 at the end of a pipe 6, which also projects into thepool of water and lies above the ring 2.- This brings the unsaturatedgases between the chlorin and the pump described below. The chlorinis'heavier than much of the gas that enters, and probably dissolves atleast slightly in the water.

The chlorin and other gases rise from the surface'of the pool andcombine in the pool and in the space above the. pool.

Through this space within the tower 4 fails a rain or continuous showerof water from Wire gauze or a foraminous plate 7 at the top of thetower. The plate may be furnished with holes of the size and shapeformed by driving an ordinary 6 wire nail through tin; such holes atinch intervals from a, satisfactory shower. This rain of water keeps thetemperature uniform throughout the tower above the pool. The 85 incomingwater may overflow from the pool into a second tank or pool 8 through apipe 9 in the side of the tank 3 and be drawn from said second tank 8 bya pump 9 through a pipe 10. This pump may be made of earthenware orother suitable material, or may include an acid egg. I have, however,foufid that an ordinary iron and steel piston pump will standconsiderable service without showing signs of corrosion where the gascombining with the chlorin is maintained in suflicient quantity. Thewater drawn from the pool is forced up through a pipe 11, to a tank 12,which may contain a heating or cooling coil 13. The water is fed fromthe upper tank 12, to the shower plate 7 through a valved pipe 14:. Thetank 12 may include a valved supply 15 from a water main, and the tank8may be furnished with an overflow 16, to carry off any surplus. 105

The tower 4 may include an outlet pipe 17 at one side" near the top withwhich is connected a, reflux condenser 18, having a ipe 19 to lead anycondensed liquid back eneath the surface of the pool in the tub 3. 110

As the stated gases and chlorin unite in the pool and in the tower abovethe pool, they form a hea liquid. This is useful as a solvent and itough volatile is heavier than water, so that when it-conden'ses thewater floats on its surface and seals the heavy While I havedescribedthe apparatus as bein used with water for the cooling agent, itwi 1 be apparent that the apparatus is equally adapted to be used withthe heavy liquid itself as a cooling, diluting or solvent agent, and theresults ma be the same, since water is a solvent of ob orin, butapparently not to any extent a. solvent of the gases used in the aboveprocess as described in detail, while the above-described heavy liquidap parently dissolves chlorin and the gases to about the same extent:

Where nearly pure chlorin is used and water is emplo ed to control thetemperature, the most esirable temperature for the particular processherein described seems to be about 15 C. At this temperature practicallyall of the unsaturated gases seem to be quickly and com letely saturatedwith chlorin by simple a ditionv reactions, while almost no substitutionproducts seem to be formed. This may be partly due to having thereactions take place in a perfectly dark towerr If chlorin from theDeacon process is used containing a very large admixture of air, itseems better to maintain the temperature in the tower at about 50 C. Inthis case the air introduced with the chlorin outlet pipe 1 form asuitable gas for fuel,

or other purposes. Substitution, products can be made from such gases bytreating them. with chlorin in the'presenoe of light as a mercury vaporlam For convenience I have called the aboveescribed process the showerbath process of treating gases. The product can be fractioned orotherwise so arated for further treatment.

believe that the product which I have obtained by pyrolizing oilscontains 4 and 5 and 6 carbon atom unsaturated com )OllIKlS having oneor more double bonds. l\ y present shower bath process furnishes anadmirable means for adding chlorin to such compounds and controlling anyrearrangement of the double bonds or other groups of atoms.

This bath will be found of practical use in the manufacture of chlorinor bromin derivatives or additionproducts from unsaturated carboncompounds as a step in the manufacture of artificial rubber.

For example, chlorin can be added to trimethylethylene. The product ofthis can be heated with a catalytic such as barium chloride to formdiolefins, of which isoprene will be one product.

Among other products of my shower bath process a hydrochloride ofethylene chloride seems to be formed, probably having the formula Whenthis is treated with lime or other alkali in excess, the hydrochloricacid breaks off, giving a parently a nearly pure ethylene chloride ofefinite boiling point 82 C.

-I have also found that among the products obtained by treatingpyrolyzed oils with chlorin in my shower bath process are tetrachlorethane (acetylene tetrachlorid) and tetrachlor propane which are usefulboth in themselves and as starting points for other products. When theseare treated with alkalies, such as lime in excess, one hydrochloric acidsplits off forming trichlor products of which CChzCHCl is the type.

Still another product which usually is formed in very small amounts is-a waxy product, hexachlor ethane, COL-CO1 which is non-inflammable andhas its melting and boiling oints near 206 C.

This wax is li i'eproof and can be refined b recrystalliz tion fromsolvents. The above-mentione low boiling point product or even ordina ykerosene oil is a suitable solvent for t 's purpose. .1

I have also found that the fraction boiling at over 125 C. of the heavyliquid, as carried out -with pyrolized petroleum and chlorin, forms anexcellent substitute for spirits of tur entine. For instance, suchfractions can e used in place of turpentine in varnishes. Such varnisheswill be noninflammable.

This same fraction will also serve as a paint remover, or the base ofone.

It seems inadvisable to carry distillation crude heavy liquid.

WVhile I have described in great detail certain features of myinvention, it will be understood that I have done so to enable thoseskilled in the art to appreciate some of its advantages, and what Iclaim as my invention is:

1. The process which comprises bubbling a complex mixture of saturatedand unsaturated hydrocarbon gases beneath the surface of a temperaturecontrolling liquid, simultaneously but separately bubbling beneath saidsurface a halogen with which said unsaturated gas will react to form anew product, allowingthe volatile parts to rise through a rain ofsaid-liquid, and collect ing the product separately from the unacted ongases.

'2. The process of obtaining a chlor ne containing product whichcomprises passing a mixture of gases including saturated and unsaturatedhydrocarbon compounds, and chlorine into a s ace through whicha tem:perature control ing liquid is raining, and removing the chlorinecontaining product separate from the other substances present.

,3. The process of obtaining a product which comprises passingunsaturated gases and a halo en into a spacethrough which a shower 0temperature-controlling liquid is raining, and removing the product.

4. The process of obtaining a product which comprises passingunsaturated carbon gaseous compounds and a halogen into a dark spacethrough which a shower of temperature-controlllng liquid is raining, andremoving the product.

5. The process of obtaining a product which comprises pyrolizing oils toproduce com lex mixtures of unsaturated and saturated carbon gaseouscompounds, then passing such gases, together with a halo-gen into a darkspace through which a shower of temperature-controlling water is rainingto produce a new product, and removing said product separately from theunacted o-n gases.

'6. The process which comprises bringing together chlorine andunsaturated hydrocarbon gases by bubbling them through a temperaturecontrolling liquid simultaneously and separately but near each other,and letting such gases as do not combine beneath the surface rise fromthe surface through a rain of such temperature controlling li uid.

7. T e process which comprises pyrolizing oils to produce a complexmixture of unsaturated and saturated gaseous carbon compounds, bringingsaid mixed gases into the presence of a halogen beneath the surface of atemperature-controlling liquid allowing the volatile parts to risethrough a rain of said liquid, so that they there combine to form a newproduct, and collecting the product separately from the unacted ongases.

8. The process which comprises pyrolizing Oils to produce a complexmixture of unsaturated and saturated gaseous carbon compounds, bringingsaid mixed gases into the presence of a gas with which the unsaturatedgases will react to combine in the presence of a:rain oftemperature-controlling liquid to form a new product, and collecting theproduct of such reaction separately from the unacted on gases.

9. The process of obtaining a product which comprises pyrolizing oils toform a complex mixture of saturated and unsaturated gaseous carboncompounds, passing said gases and chlorine into a pool oftemperature-controlling liquid, so that the unacted on gases risethrough a rain of temperaturecontrolling liquid to obtain a new product,and recovering the product separately from the unacted on gases.

10. The process of separating saturated from unsaturated gaseous carboncompounds in a mixture of gases which comprises passng themixture intothe presence of chlorin in a ram of water, and permitting any saturatedgases to pass off while the unsaturated gases take up chlorin and fallas a'liquid.

'11. The combination with a substantially dark chamber of a pool oftemperature-controlling liquid at the bottom thereof, means I 12. Thecombi ation with a chamber, of a pool of tempe ature-controlling liquidat the bottom :he I 'eof, means for removing liquids from aid pool,means for admitting a corrosive gas beneath the surface of said .pool,means for admitting a non-corrosive gas beneath the surface of said poolbetween the corrosive gas and the removing means, an escape duct foruncombined gases above said pool, and means for showering said liquidthrough the space above said pool.

13. The process of making a 'chlorlne con- .taining compound whichcomprises bringin together unsaturated hydrocarbon gas an chlorine inthe presence of sufiicient water in a finely divided state to controlthe tempera ture and removing the product separated from any unacte'd ongas.

14, The process of making a complex mixture of chlorine containin carboncompounds which comprises brlnging together complex mixed unsaturatedand saturated hydrocarbon gases and chlorine in the presence of Water ina finely divided state, and removin the unacted on gases separate fromthe ch orine containing product.

15. The process of making chlorine containing car on compounds whichcomprises bringing acomplex mixture of gases com prising saturated andunsaturated hydrocarbons to ether with chlorine in the presence of sucient Water in a finely divided state to control the temperature, andremoving the products separately from any unacted on gas. I

16. The process which comprises bringing together unsaturated gaseouscarbon compounds of the ethylene series and chlorine in the resence ofthe product formed by their com ination.

GAIL MERSEREAU.

